Metal working lubricant



ivmrxr wonmu LUBRICANT Stewart J. Beaubien, flakland, Thomas E. Reamer,El Cerrito, and Paul H. Williams, Orintla, Califi, assignors to ShellDevelopment Company, New York, N. Y., a corporation of Delaware NoDrawing. Application February 3, 1955 Serial No. 486,032

3 Claims. (Cl. 252-325) This invention relates to improved lubricatingcompositions, and more particularly to aqueous lubricating compositionsadapted for various metal cutting and fabrieating operations.

The class of water-soluble non-ionic surface active agents availablecommercially under the trade name Pluromcs, marketed by the WyandotteChemical Corporation and of the class of polyoxyalkylene diols describedin U. S. Patents 2,674,619 and 2,677,700, have been suggested assuitable lubricants for water-base metal working lubricants. Althoughcutting fluids containing these surface active agents are excellent asfar as cutting and load carrying properties are concerned, it has beenfound that they cause sticking of machine tool ways, resulting in a slowdown, or under aggravated conditions, even in stoppage of production.The reason for this phenomenon is not understood but it appears that itmay be attributable to the presence of the hydrophobic homopolymericpolyoxyalkylene unit representing essentially a substantial portion ofthe molecule. Increasing the water-solubility by incorporating a largerproportion of water-soluble alkylene oxide groups in compounds of thistype does not obviate the above undesirable properties which compoundsof the above type possess.

The principal object of this invention is to provide an improved aqueousmetal-working lubricant. A further object is to provide an aqueous baseconcentrate suitable as a metal-working lubricant and adapted to bediluted with water to an improved metal working lubricant.

It has now been discovered that the objects of the present invention areattained by a substantially aqueous medium containing a minor amount of(I) a water-soluble heteric copolymeric alkylene glycol, ether or esterthereof, wherein the diiferent oxyalkylene units are substantiallyrandomly distributed throughout the entire polyoxyalkylene chain, and(II) a minor proportion of a water-soluble polyoxyalkylene compoundcontaining a hydrophobic homopolyoxyalkylene unit, of the type describedin the above mentioned U. S. Patents 2,674,619 and 2,677,700. Thesepolymeric agents are block copolymers or cogeneric mixtures ofconjugated polyoxyalkylene compounds containing at least one hydrophobichomopolyoxyalkylene unit of a unit weight of at least 800, andpreferably 900, and one or two other hydrophilic polymeric unit(s) whichcomprise about to about 90% of the total polymeric compound.

The heteric copolymeric compounds (I) are available commercially underthe trade name of Ucons and sold by Carbide and Carbon Chemical Companyand are fully described in U. S. Patent 2,425,845. The manner in whichthese compounds (1) function in overcoming the sticking properties ofthe other type of polymer (II) is not clearly imderstood. Both polymericmaterials (I) and (II) have been suggested in publications and priorpatents as additives for metal working compositions. However, polymersof type (I) lack load carrying properties and are therefore relativelyuseless! States Patent where extreme pressures, wear and loads areencountered and are also excessively corrosive. However, applicants havediscovered that the combination of the difierent types of polymericcompounds (I) and (H) in an aqueous base, provides a lubricant in whichthe shortcomings of each additive are overcome by the presence of theother; the desirable properties of each are accentuated and the resultis an aqueous metal working lubricant which is stable, non-corrosive,does not cause sticking and is capable of carrying loads far in excessof similar compositions but in which either type of additive is omitted.

The heteric copolymeric compounds (I) are watersoluble relatively highmolecular weight copolymers containing no substantially hydrophobicpolyoxyalkylene units or chains, the polymer being composed of randomlydistributed (heteric) oxyethylene and oxy 1,2-propylene groups in themolecule. Polymers of this type are suitably prepared by the methodsdescribed in U. S. Patent 2,425,845, as by reacting aliphatic diols orglycols simultaneously with ethylene oxide and 1,2-propylene oxide. Theterm heteric is used to designate an internal configuration of randomdistribution of the units making up the copolymer, as distinguished froma group ing of such oxyethylene and oxypropylene units, in homopolymericunits, with those of oxypropylene being of sufiicient degree ofpolymerization to exhibit a substantially hydrophobic character, as inthe case of type II polymers.

A suitable method of preparing these heteric copolymers is to chargeabout 25 to parts of 1,2- propylene glycol and from about 10 to partsethylene oxide into a suitable reactor and react the mixture in thepresence of a caustic catalyst, such as sodium hydroxide. To the mixturea diol such as diethylene glycol is added and the mix is heated to aboutC. to C. at from 5 to 75 p. s. i. After the reaction is (completed, thereaction mixture is neutralized with carbon dioxide and hot waterwashed. The diol composition phase is dissolved in dichloro diethylether and its lowboiling constituents removed by stripping.

EXAMPLE I A polymeric product of type (I) is prepared by reacting amixture of 75 parts of ethylene oxide, 25 parts of 1,2-oxypropylene, 20parts of diethylene glycol and 1 part of sodium hydroxide. The mixturewas heated for 2-4 hours at a temperature of ll0-l25 C. and a pressureof 6-40 p. s. i. The product was purified by distillation to removevolatile fraction and filtration to remove sodium hydroxide and had thefollowing properties: average molecularweight 1,108; specific viscosityat 18 0., 0.1811; density, 210 R, 1.0296; refractive index 20 C./D1.4671; flash temperature, 446 F; viscosity, centistokes at 210 F.,17.5; and is water-soluble in all proportions.

The second of the polymeric compounds (H) is a block copolymer orcogeneric mixture containing substantially a hydrophobic polyoxyalkyleneunit such as polyoxypropylene unit of at least 800 and preferably 900unit weight and the balance, which comprises from 15 to 90% of the totalmolecule, being hydrophilic polyoxyalkylene unit or units such aspolyoxyethylene units. Copolymers of this type can be prepared by themethods described in U. S. Patents 2,674,619 and 2,677,700. Essentially,these polymeric compounds can be prepared by first condensing analkylene oxide having from 3 to 8 carbon atoms such as propylene oxidewith an organic base compound containing a single or plurality ofreactive hydrogen atoms to form a hydrophobic polyoxyalkylene polymersuch as polyoxypropylene polymer of at least 800 and preferably 900molecular weight and thereafter condensing said polymer with ethyleneoxide so as to form thereon hydrophilic 3 nelye ye hylene nitts), whichcomprise from about o a u f he total polymer- In preparing thepolyoxypropylene polymer, the condensation of propylene oxide with thereactive hydrogen organic compound is normally carried out at elevatedtemperatures and pressures in the presence of an alkaline catalyst suchas sodium alkoxide, a quaternary ammonium base, or sodium hydroxide.Similarly, the condensation reaction may be carried .out in the'presenceof acid catalysts as set forth in U. S. Patent No. 2,510,540.

Although the reaction may be carried out by simply heating a mixture ofthe reactants under pressure at a suf ficientlyhigh temperature thisprocedure is not ordinarly used as the temperatures and pressuresrequired are excessive and control of the exothermic reaction isdiificult.

The preferred method of carrying out the reaction is to add thepropylene oxide to a stirred, heated mixture of the desired reactivehydrogen compound and alkaline catalyst in a sealed reaction vessel. Byadding the propylene oxide to the reaction vessel at such a .rate thatit reacts as rapidly as added, an excess of propylene oxide is avoidedand control of the reaction is simplified.

The temperature at which the reaction is run will depend upon theparticular system in question and especially upon the catalystconcentration used. Generally, at higher catalyst concentrations thereaction can be run at lower temperatures and correspondingly lowerpressures. The temperatures and pressures required for any givenreaction will vary with the reactive-hydrogen compound, and the type andconcentration of catalyst used.

The condensation of ethylene oxide with the polyoxypropylene polymer iscarried out in an analogous manner.

The preparation of the type II block polymeric polyoxyalkylene compoundis illustrated in Example II.

EXAMPLE II.PART A In a one-liter 3-neck round bottom flask equipped witha mechanical stirrer, reflux condenser, thermometer and propylene oxidefeed inlet, there were placed 57 grams (0.75 mol) of propylene glycoland 7.5 grams of anhydrous sodium hydroxide. The flask was purged withnitrogen to remove air and heated to 120 C. with stirring, and until thesodium hydroxide was dissolved. Then sufficient propylene oxide wasintroduced into the mixture as fast as it would react until the productpossessed a calculated molecular weight of 2380. The product was cooledunder nitrogen, the NaOl-I catalyst neutralized with sulfuric acid andthe product filtered to remove inorganic solids. The final product was awater-insoluble polyoxypropylene glycol having an average molecularweight of 1620 as determined by hydroxyl number or acetylationanalytical test procedure.

EXAMPLE II.PART B The foregoing polyoxypropylene glycol, having anaverage molecular weight of 1620, was placed in the same apparatus asdescribed in Part A of this example, in the amount of 500 grams (0.308mol), to which there was added 5 grams of anhydrous sodium hydroxide.One hundred and five grams of ethylene oxide was added to an averagetemperature of 120 C., using the same'technique as employed in Part A.The amount of added ethylene oxide corresponded to 17.4% of the totalweight of the polyoxypropylene glycol base plus the weight of addedethylene oxide.

Polyoxypropylene is prepared by condensing propylene oxide with arelatively low molecular weight organic compound containing a pluralityof reactive hydrogen atoms. The function of this base compound is tofurnish reaction hydrogen atoms which initiate the polymerization of thepropylene oxide'and since the base compound constitutes only a smallproportion of the resulting high molecular weight polyoxyalkylenecompounds, it ordinarilydoes not have an influence onthe propertiesthereof. In other words,-the particular base compound'employed inpreparing the polyoxyalkylene compounds is not critical so long as itfurnishes at least one reactive hydrogen atom, and operablepolyoxyalkylene compounds are obtained regardless of the particular basecompound employed in the preparation of the polyoxypropylene polymer.Ordinarily it is preferred to employ relatively low molecular weightbase compounds, e. g., less than 200 molecular weight, preferablypolyhydric alcohols, such as ethylene glycol, propylene glycol, butyleneglycol, trimethylene glycol, glycerol, and the like, usually a monomericsubstance, although dimers, such as diethylene glycol and dipropyleneglycol are suitable.

EXAMPLE III positions of the resulting compounds are set forth in TableI.

Table I l Moleoulm- Polycry- Weight ethylene Polyoxy- Content, BaseCompound propylene Percent of Polymer Compound (water- (wateriusoluble)soluble) Acetamide, 974 i 36 1,5-pentanediol l, 372 50 Glyeerine 2, 06048 Sucrose, 5, 060 4-9 Ethylene diamine 1, 850 50 Ben'zenesulfonamide 1,179 50 In many cases the addition of solubilizing or coupling agents tocompositions of this invention is desirable. Suitable agents of thistype include: glycol-ethers, such as diethylene glycol momomethyl,ethyl, n and isopropyl ethers, diethylene glycol mono-butyl ether,diethylene glycol mono-.decyl ether, dipropylene glycol monoethyl ether,dipropylene glycol mono-isopropyl ether, dipropylene glycolmonodsoamylether, diisobutylene glycol-mono isopropylether, etc. Instead oftheglycol-ethers, various alcohols may be used, such as diols having 6 ormore carbon atoms in the molecule, e. g., hexylene .glycol, decyleneglycols,- cetylene glycols, etc.; diglycols such as dipropyleneglycols,-dibutylene glycol, diamylene glycol, ether alcoholsandparticularly the glycol monalkyl ethers, "eg., Carbon and CarbideChemical Corp. Carbitols and el osol s su h a t y glycol monohyl ther.ethylene glycol mono-propyl ether, ethylene glycol monon-bu y et er, e he eg y o mo yl h r, ethylene glycol mono-.tert-butylether, ethyleneglycol mono? hexyl-butyl ether, propylene glycol mono-isoamyl ether,

etc.

When necessary, corrosion inhibitors can be used in compositions of thisinvention of which appreciably watersoluble inorganic or organicnitrites and/or aminessuch as alkyl or alkylolamines, and mixturesthereof are particularly preferred.

' The nitrites include the metal nitrites such as sodium,potassium,lithium, calcium and barium nitrites, of which the alkalimetal nitrites are preferred; also, the organic base nitrites maybeused, preferably the organic nitrogen base nitrites, such asbenzyl-trimethylammonium nitrite, morpholiniu n nitrite,dibenzylammonium nitrite, 3,3,5- trimethylcyclohexylammonium nitrite,cyclo-hexylam noiutn n ite, b a-phenyl t y m ni nitr t 2,4,5-tetramethyl tetrahydro 1,3-oxazonium nitrite, methyl isobutylcarbammonium nitrite, piperidinium nitrite, dicyclohexylammoniumnitrite, dicyclohexyl isopropylammonium nitrite, and their homologuesand analogues, as well as mixtures containing these and other corrosioninhibitors.

The amines include alkyl and alkyloamines such as mono-, diandtriethyl-, propyl-, butylamine; mono, diand tri-ethanolamines,dimethyl-ethanolamines, diethylethanolamines, aminoethyl-ethanolamiue,mono-, diand tri-isopropylamine, methyl-diethanolamine, N-acetylethanolamine, phenylethanolamine, phenyl-diethanolamine and mixturesthereof.

If desired, oiliness or specific types of anti-wear agents can be addedin minor amount to compositions of this invention of which fatty acidsand particularly unsaturated fatty acids are most suitable. Among suchacids are included saturated acids, e. g., capric, lauric, myristic,palmitic, stearic acids; unsaturated acids such as palmoleic, oleic,ricinoleic, erucic, linoleic, linolenic acids and mixtures thereof.These acids are stabily dispersed in the water base apparently by theaid of the block polymers 1!.

Minor amounts of anti-foaming, masking, bactericidal and anti-corrosiveagents for copper and copper alloys, and/r perfuming agents, may beadded to improve the composition. Among such materials may be included:anti-foaming agents, e. g., organic silicone compounds illustrated bydimethyl silicone polymer; phosphates, e. g., tributyl phosphate, alkalimetal polyphosphates illustrated by sodium alkyl polyphosphates;polyglycidiisopropyl other (mol. wt. 500-1200, preferably 600-800);masking agents, e. g., low molecular weight aldehydes (acetaldehyde);oil of pines, oil of mirbane; bactericides, e. g., alkyl phenols andphenates such as sodium o-phenyl phenate; and copper anti-corrosionagents, e. g., mercaptobenzothiazoles (sodium mercaptobenzothiazole),and the like.

Efiective metal working lubricant concentrates, in accordance with thepresent invention, are preparable according to the followingformulations:

Broad Pre- Range, fer-red percent Range, wt. percent EssentialAdditives:

Ablock polymer comprising a mixture of a polymeric compound (II)containing a hydrophobic polyoxyalkylene unit; of at least 800 mol wt.made by polymeric alkylene oxides of from 3 to 8 carbon atoms andpolyoxyethylene units comprising 15-90% of the total polymer 5-20 6-10 Arandomly distributed water-soluble polyoxypropylene-polyoxyethylenecopolymer (1) having substantially no hydrophob units 5-2O 6-15Preferred Additives:

1. Corrosion inhibitors e. g., inorganic nitrites,

alkylolamiucs and mixtures 1-12 5-10 2. Anti-wear agents, fatty acids,e. g., oleic acid. 0. 01-5 0. 5-3 Optional Additives: Anti-foamingagents, coupling agents, germicidal agents, etc 0. 01-20 0.1-12 Base:

Water Balance Balance Illustrative examples of metal workingconcentrates of this invention comprise:

Composition A: Ferceut Additive of Example I Addition of Example II 3Sodium nitrite 8 Triethanolamine 8 Hexylene glycol 10 Oleic acid 1Sodium mercaptobenzothiazole (in 50% water)- 0.5 Sodium o-phenylphenate1 Sodium alkyl polyphosphate 1 Water Balance Composition B:

Additive of Example I 10 Additive of Example H 8 Sodium nitrite 8Trisodium phosphate 8 Water Balance Composition C:

Additive of Example I 8 Additive of Example II 8 Sodium nitrite 8Ethanolamine 8 Water Balance Composition D:

Additive of Example I 10 Additive of Example H 10 Sodium nitrite 8Sodium borate 8 Oleic acid l Dimethylethanolamine 8 Water BalanceComposition E:

Additive of Example I l0 Additive of Example II 10 Sodium nitrite 8Linoleic acid 2 Triethanolamine 8 Sodium mercaptobenzothiazole (in 50%water)- 0.5 Water Balance Generally the concentrates can be used neutralor diluted with from 1 to parts of Water depending upon the use to whichit is put. For cutting of steel, dilutions of 1:20-1:40 are recommended.For cutting of cast iron 1:10-1:20, while for grinding operationsdilutions with water of 1:40-1:50, can be used.

Compositions of this invention are outstanding metal working lubricants.For example, composition A (at 1:20 dilution with water) was compared bytest to a similar composition but in which additive Example 11 wasomitted (composition X). Composition A showed an increase of 54% indrill life over composition X, and a decrease in sliding friction offrom 500 g. to g. over composition X. Also, composition A, when used asa coolant on a lathe in a commercial plant caused no corrosion of metalparts with which it came in contact and the lathe was clean and itsworking parts were in excellent condition even after weeks of use.However, when a similar composition was used, but in which additive ofExample I was omitted (composition Y) in the same machine and operation,the sliding parts of the lathe became sticky and after a day the machinehad to be stopped and cleaned.

Compositions of this invention can be applied with ex cellent results togeneral cutting operations where cooling and lubrication of the tool andwork piece under adverse conditions are encountered. Metals machinedwith the aid of fluids of this invention have good surface finish, arefree from rust and stain, and the total life of machine tools and fluidis excellent.

We claim as our invention:

1. A metal Working lubricating concentrate comprising a Water basecomposition containing from about 5% to about 20% each of (1) a blockcopolymer of polyoxypropylene polyoxyethylene compounds containing intheir structure hydrophobic oxypropylene groups, hydrophilic oxyethylenegroups and an organic radical derived from an organic compoundcontaining a reactive hydrogen atom; the compounds being characterizedin that all of the oxypropylene groups are present in polyoxypropylenechains that are attached to the organic radical at the site of areactive hydrogen atom thereby constituting a hydrophobicpolyoxypropylene polymer, the oxyethylene groups being attached to thepolyoxypropylene polymer. in polyoxyethylene chains, the averagemolecular Weight of the hydrophobic .polyoxypropylene polymers in themixture being at least 900, as determined by hydroxyl number, and theoxyethylene groups present constituting -90% by weight, of total block.copolymers, and (2) a mixture of heteric oxyethylene-oxy 1,2-propylenediols in which ethylene oxide and 1,2-propylene oxide are combinedtherein as oxyethylene and oxy 1,2-propylene groups in a ratio which isat least one-third part of 1,2-propylene oxide for each part of ethyleneoxide, by weight, said diols containing in a single molecule both theoxyethylene and the .oxy 1,2-propylene groups and said'mixture having anaverage molecular Weight of at least 300 attributable to said groups,from about 1% to 12% each of (3) sodium nitrite and an ethanolamine andfrom about 0.01% to about 5% of (4) an unsaturated high molecular Weightfatty acid.

2. A metal working lubricating concentrate comprising a water basecomposition containing from about 5% to about each of (1) a blockcopolymer of polyoxypropylene-polyoxyethylene containing in theirstructure oxypropylene groups, oxyethylene groups and an organic radicalderived from an organic compound containing a plurality of reactivehydrogen atoms; the cornpounds being characterized in that allot theoxypropylene groups are present in polyoxypropylene chains that areattached to the organic radical at the site of a reactive hydrogen atomthereby constituting a hydrophobic polyoxypropylene polymer; theoxyethylene groups being ati tached to the polyoxypropylene polymer inhydrophilic polyoxyethylene chains; the average molecular weight of thehydrophobic polyoxypropylene polymers in the mixture being at least1600, as determined by hydroxyl number, and the oxyethylene groupspresent constituting I t -60% by Weight, of the mixture, and (2) amixture of heteric oxyethylene-oxy 1,2-propylene diols in which ethyleneoxide and 1,2-propylene oxide are combined therein as oxyethylene andoxy 1,2-propylene groups in a ratio which is at least one-third part of1,2-propylene oxide for each part of ethylene oxide, by weight; saiddiols containing in a single molecule both the oxyethylene and the oxy1,2-propy1ene groups and said mixture having an average molecular weightof at least 300 attributable to said groups; from about 1% to 12% eachof (3) sodium nitrite, (4) triethanolamine, (5) hexylene glycol, andfrom about 0.01% to about 5% each of (6) oleic acid, (7) sodiumo-phenylphenate, (8) sodium alkyl polyphosphate and (9) sodiummercaptobenzothiazole.

3. A metal working lubricating concentrate consisting essentially of awater .base composition containing: 1) 10% of a block copolymer ofpolyoxypropylene-polyoxye'thylene containing in its structureoxypropylene groups, oxyethylene groups and 'an organic radical derivedfrom an organic compound containing a-plurality of reactive hydrogenatoms, the copolymer being characterized in that all of the oxypropylenegroups are present in polyoxypropylene chains that are attached to theorganic radical at the site of a reactive hydrogen atom therebyconstituting a hydrophobic polyoxypropylene polymer structure, theoxyethylene groups being attached to the polyoxypropylene polymer"structure in hydr0- philic polyoxyethylene chains, the averagemolecular weight of the hydrophobic polyoxypropylene polymer structureinthe copolymer being at least 1600, as determined by hydroxyl number,and the oxyethylene groups present constituting BO-% by weight of thecopolymer, (2) 8% of a mixture of heteric oxyethylene-oxy-1,2- propylenediols in which oxyethylene and oxy-1,2-propylene groups are present in aratio which is at least onethird part by weight of oxy-1,2-propylenegroups for each part by weight of oxyethylene groups, said diolscontaining in a single molecule both the oxyethylene and theoxy-1,2-propylene groups and having an average molecular weight of atleast 300 attributable to said groups, (3) 8% sodium nitrite, (4) 8%tn'ethanolamine, (5) 10% hexylene glycol, (6) 1% oleic acid, (7) 1%sodium o-phenylphenate, (8) 1% sodium alkyl polyphosphate and (9) /z%sodium mercaptobenzothiazole.

References Cited in the file of this patent UNITED STATES PATENTS2,425,845 Toussaint Aug. 19, 1947 2,692,859 Talley Oct. 26, 1954 FOREIGNPATENTS 716,354 Great Britain Oct. 6, 1954 721,526 Great Britain Jan. 5,1955

1. A METAL WORKING LUBRICATING CONCENTRATE COMPRISING A WATER BASECOMPOSITION CONTAINING FROM ABOUT 5% TO ABOUT 20% EACH OF (1) A BLOCKCOPOLYMER OF POLYOXYPROPYLENE POLYOXYETHYLENE COMPOUNDS CONTAINING INTHEIR STRUCTURE HYDROPHOBIC OXYPROPYLENE GROUPS, HYDROPHILIC OXYETHYLENEGROUPS AND AN ORGANIC RADICAL DERIVED FROM AN ORGANIC COMPOUNDCONTAINING A REACTIVE HYDROGEN ATOM; THE COMPOUNDS BEING CHARACTERISEDIN THAT ALL OF THE OXYPROPYLENE GROUPS ARE PRESENT IN POLYOXYPROPYLENECHAINS THAT ARE ATTACHED TO THE ORGANIC RADICAL AT THE SITE OF AREACTIVE HYDROGEN ATOM THEREBY CONSTITUTING A HYDROPHOBICPOLYOXYPROPYLENE POLYMER, THE OXYETHYLENE GROUPS BEING ATTACHED TO THEPOLYOXYPROPYLENE POLYMER IN POLYOXYETHYLENE CHAINS, THE AVERAGEMOLECULAR WEIGHT OF THE HYDROPHOBIC POLYOXYPROPYLENE POLYMERS IN THEMIXTURE BEING AT LEAST 900, AS DETERMINED BY HYDROXYL NUMBER, AND THEOXYETHYLENE GROUPS PRESENT CONSTITUTING 15-90% BY WEIGHT, OF TOTAL BLOCKCOPOLYMERS, AND (2) A MIXTURE OF HETERIC OXYETHYLENE-OXY 1,2-PROPYLENEDIOLS IN WHICH ETHYLENE OXIDE AND 1,2-PROPYLENE OXIDE ARE COMBINEDTHEREIN AS OXYETHYLENE AND OXY 1,2-PROPYLENE GROUPS IN A RATION WHICH ISAT LEAST ONE-THIRD PART OF 1,2-PROPYLENE OXIDE FOR EACH PART OF ETHYLENEOXIDE, BY WEIGHT, SAID DIOLS CONTAINING IN A SINGLE MOLECULE BOTH THEOXYETHYLENE AND THE OXY 1,2-PROPYLENE GROUPS AND SAID MIXTURE HAVING ANAVERAGE MOLECULAR WEIGHT OF AT LEAST 300 ATTRIBUTABLE TO SAID GROUPS,FROM ABOUT 1% TO 12% EACH OF (3) SODIUM NITRITE AND AS ETHANOLAMINE ANDFROM ABOUT 0.01% TO ABOUT 5% OF (4) AN UNSATURATED HIGH MOLECULAR WEIGHTFATTY ACID.